Chemoenzymatic Synthesis of Fluorinated Cellodextrins Identifies a New Allomorph for Cellulose-Like Materials**

Understanding the fine details of the self-assembly of building blocks into complex hierarchical structures represents a major challenge en route to the design and preparation of soft-matter materials with specific properties. Enzymatically synthesised cellodextrins are known to have limited water solubility beyond DP9, a point at which they self-assemble into particles resembling the antiparallel cellulose II crystalline packing. We have prepared and characterised a series of site-selectively fluorinated cellodextrins with different degrees of fluorination and substitution patterns by chemoenzymatic synthesis. Bearing in mind the potential disruption of the hydrogen-bond network of cellulose II, we have prepared and characterised a multiply 6-fluorinated cellodextrin. In addition, a series of single site-selectively fluorinated cellodextrins was synthesised to assess the structural impact upon the addition of one fluorine atom per chain. The structural characterisation of these materials at different length scales, combining advanced NMR spectroscopy and microscopy methods, showed that a 6-fluorinated donor substrate yielded multiply 6-fluorinated cellodextrin chains that assembled into particles presenting morphological and crystallinity features, and intermolecular interactions, that are unprecedented for cellulose-like materials.     

On the Coherent Description of Diffusion‐Influenced Fluorescence Quenching Experiments II: Early Events

In a previous article we showed how to perform and analyze steady‐state and nanosecond time‐resolved experiments on fluorescence quenching by electron transfer in a coherent manner. Now, by making use of a superior time resolution, we explore the first stages of this kind of reaction. The novel information gained enables us to merge the results on the viscosity and the driving‐force dependencies of the reaction rate. A unique set of parameters for a single reaction channel suffices to describe all the results in the frame of differential encounter theory for diffusion‐influenced, bimolecular, remote electron‐transfer reactions. The inclusion of the solvent structure is crucial for the understanding of the reaction kinetics. To the authors’ best knowledge, this is the first time that such a comprehensive set of data has been successfully and jointly explained in the field, with physically sound parameters for electron‐transfer reactions.     

Ligand–Receptor Binding Affinities from Saturation Transfer Difference (STD) NMR Spectroscopy: The Binding Isotherm of STD Initial Growth Rates

The direct evaluation of dissociation constants (K_D) from the variation of saturation transfer difference (STD) NMR spectroscopy values with the receptor–ligand ratio is not feasible due to the complex dependence of STD intensities on the spectral properties of the observed signals. Indirect evaluation, by competition experiments, allows the determination of K_D, as long as a ligand of known affinity is available for the protein under study. Herein, we present a novel protocol based on STD NMR spectroscopy for the direct measurements of receptor–ligand dissociation constants (K_D) from single‐ligand titration experiments. The influence of several experimental factors on STD values has been studied in detail, confirming the marked impact on standard determinations of protein–ligand affinities by STD NMR spectroscopy. These factors, namely, STD saturation time, ligand residence time in the complex, and the intensity of the signal, affect the accumulation of saturation in the free ligand by processes closely related to fast protein–ligand rebinding and longitudinal relaxation of the ligand signals. The proposed method avoids the dependence of the magnitudes of ligand STD signals at a given saturation time on spurious factors by constructing the binding isotherms using the initial growth rates of the STD amplification factors, in a similar way to the use of NOE growing rates to estimate cross relaxation rates for distance evaluations. Herein, it is demonstrated that the effects of these factors are cancelled out by analyzing the protein–ligand association curve using STD values at the limit of zero saturation time, when virtually no ligand rebinding or relaxation takes place. The approach is validated for two well‐studied protein–ligand systems: the binding of the saccharides GlcNAc and GlcNAcβ1,4GlcNAc (chitobiose) to the wheat germ agglutinin (WGA) lectin, and the interaction of the amino acid L ‐tryptophan to bovine serum albumin (BSA). In all cases, the experimental K_D measured under different experimental conditions converged to the thermodynamic values. The proposed protocol allows accurate determinations of protein–ligand dissociation constants, extending the applicability of the STD NMR spectroscopy for affinity measurements, which is of particular relevance for those proteins for which a ligand of known affinity is not available.     

Development of new polyolefin films with nanoclays for application in food packaging

Nanomaterials have been demonstrated to possess novel characteristics that can be applied in developing new packaging with better properties than packaging produced with micromaterials. Such developments include the production of packaging with improved barrier properties, which applied to the food industry will extend the shelf life of a food, thereby expanding its marketing potential. The present study entailed the optimization of experimental variables (pressure, temperature, processing time, feed position, etc.) involved in the elaboration of polypropylene and polyethylene films with nanoparticles, to obtain a film with good exfoliation, barrier and mechanical properties. SEM, TEM and XRD were also evaluated as tools for determining the degree of exfoliation of nanoparticles. Optimization of the technology involved in production of an exfoliated nanocompound is a complex process in which multiple variables and parameters are involved. The results of the study showed that the feed position of the nanoparticle in the double screw extruder is of vital importance in obtaining an exfoliated film. The maximum temperatures used in the extruder were 170 °C and 130 °C, for polypropylene and polyethylene respectively.     

Maximum-entropy analysis of atomic compton profiles

The maximum-entropy formalism is used to obtain approximations to the atomic Compton profile, ??(q), in terms of the first few radial expectation values 〈Pⁿ〉 of the momentum density γ(p). This method leads to the least-biased results by the information not used. In particular, analytical and numerical approximations to the kinetic energy T and to the height of the peak ??(O) and the half-width q_0.5 of the Compton profile are obtained. Our results generalize and improve some approximations to ??(q) previously obtained by other authors. For illustration, the accuracy of these approximations are studied by means of near-Hartree–Fock wave functions. © 1995 John Wiley & Sons, Inc.     

Information entropies of many-electron systems

The Boltzmann–Shannon (BS ) information entropy S_ρ = ∫ ρ(r)log ρ(r)dr measures the spread or extent of the one-electron density ρ(r), which is the basic variable of the density function theory of the many electron systems. This quantity cannot be analytically computed, not even for simple quantum mechanical systems such as, e.g., the harmonic oscillator (HO ) and the hydrogen atom (HA ) in arbitrary excited states. Here, we first review (i) the present knowledge and open problems in the analytical determination of the BS entropies for the HO and HA systems in both position and momentum spaces and (ii) the known rigorous lower and upper bounds to the position and momentum BS entropies of many-electron systems in terms of the radial expectation values in the corresponding space. Then, we find general inequalities which relate the BS entropies and various density functionals. Particular cases of these results are rigorous relationships of the BS entropies and some relevant density functionals (e.g., the Thomas–Fermi kinetic energy, the Dirac–Slater exchange energy, the average electron density) for finite many-electron systems. © 1995 John Wiley & Sons, Inc.     

Spreading measures of information-extremizer distributions: applications to atomic electron densities in position and momentum spaces

The problem of finding the information-extremizer distribution with a set of given constraints (partial information) has a relevant role from both physical and chemical points of view, specially when working within a density functional theory framework. Beyond the variance, there exist different measures of information susceptible of being extremized, such as the Fisher information and the Shannon and Tsallis entropies. Each one possesses its own properties which make their use more or less convenient according to the systems and/or the process we are dealing with. In this work, we analyze the main information measures of the electron densities of neutral atoms throughout the periodic table, in the two conjugated position and momentum spaces. It is shown how these measures display shell-filling patterns, within a level which depends on the information measure and the space considered. Additionally, the values of all these measures for the solution of various atomic information extremization problems (MaxEnt, MaxTent, MinInf), using radial expectation values as constraints, are analytically obtained, numerically evaluated and also interpreted and discussed in terms of physical characteristics of the atomic systems, such as periodicity and shell structure.     

New low-energy measurement of the 18F(p,α)15O reaction

The ¹⁸F, produced during nova explosions, is the main responsible for the 511 keV γ-ray emitted during the outburst that could be detected with satellite missions or future γ-ray telescopes. In spite of many experimental efforts, the amount of ¹⁸F synthesized still suffers from large uncertainties concerning mainly the ¹⁸F(p,α)¹⁵O reaction. We report here on a new direct measurement of the ¹⁸F(p,α)¹⁵O cross section recently carried out at the RIB facility at Louvain-la-Neuve. Cross section data down to a center-of-mass energy of 400 keV have been obtained using an isobarically pure ¹⁸F beam (averaged intensity of the order of 10⁶ pps) and a thin polyethylene target. The reaction products were detected using the multi-strip detector array LEDA. The cross section data are analysed in the framework of the R-matrix model. Our main aim is to determine the interference sign between three 3/2⁺ resonances above threshold that can significantly affect the extrapolation of the ¹⁸F(p,α)¹⁵O cross section to the energies relevant for novae, and thus, the modeling of nova explosions.     

Direct measurement of the 14N(p,gamma)15O S factor

The 14N(p,gamma)15O reaction regulates the rate of energy generation in the stellar CN cycle. Because discrepancies have been found in the analysis and interpretation of previous capture data, we have measured the 14N(p,gamma)15O excitation function for energies in the range E(lab)(p)=155-524 keV. Fits of these data using R-matrix theory yield a value for the S factor at zero energy of 1.68+/-0.09(stat)+/-0.16(syst) keV b, which is significantly smaller than the previous result. The corresponding reduction in the stellar reaction rate for 14N(p,gamma)15O has a number of interesting consequences, including an impact on estimates for the age of the Galaxy derived from globular clusters.     

Bifurcations of non-smooth systems

Non-smooth systems (namely piecewise-smooth systems) have received much attention in the last decade. Many contributions in this area show that theory and applications (to electronic circuits, mechanical systems, …) are relevant to problems in science and engineering. Specially, new bifurcations have been reported in the literature, and this was the topic of this minisymposium. Thus both bifurcation theory and its applications were included. Several contributions from different fields show that non-smooth bifurcations are a hot topic in research. Thus in this paper the reader can find contributions from electronics, energy markets and population dynamics. Also, a carefully-written specific algebraic software tool is presented.